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Emergent magnetic phenomena at interfaces represent a frontier in materials science, pivotal for advancing technologies in spintronics and magnetic storage. In this letter, we utilize a suite of advanced X-ray spectroscopic and scattering techniques to investigate emergent interfacial ferromagnetism in oxide superlattices comprised of antiferromagnetic CaMnO3 and paramagnetic CaRuO3. Our findings challenge prior theoretical models by demonstrating that the ferromagnetism extends beyond the interfacial layer into multiple unit cells of CaMnO3 and exhibits an asymmetric profile. Complementary density functional calculations reveal that the interfacial ferromagnetism is driven by the double exchange mechanism, facilitated by charge transfer from Ru to Mn ions. Additionally, defect chemistry, particularly the presence of oxygen vacancies, likely plays a crucial role in modifying the magnetic moments at the interface, leading to the observed asymmetry between the top and bottom CaMnO3 interfacial magnetic layers. Our findings underscore the potential of manipulating interfacial ferromagnetism through point defect engineering.

Ultrafast electric-field control of emergent electronic and magnetic states at oxide interfaces offers exciting prospects for the development of new generations of energy-efficient devices. Here, we demonstrate that the electronic structure and emergent ferromagnetic interfacial state in epitaxial LaNiO3/CaMnO3 superlattices can be effectively controlled using intense single-cycle THz electric-field pulses. We employ a combination of polarization-dependent X-ray absorption spectroscopy with magnetic circular dichroism and X-ray resonant magnetic reflectivity to measure a detailed magneto-optical profile and thickness of the ferromagnetic interfacial layer. Then, we use time-resolved and temperature-dependent magneto-optical Kerr effect, along with transient optical reflectivity and transmissivity measurements, to disentangle multiple correlated electronic and magnetic processes driven by ultrafast high-field (~1 MV/cm) THz pulses. These processes include an initial sub-picosecond electronic response, consistent with non-equilibrium Joule heating; a rapid (~270 fs) demagnetization of the ferromagnetic interfacial layer, driven by THz-field-induced nonequilibrium spin-polarized currents; and subsequent multi-picosecond dynamics, possibly indicative of a change in the magnetic state of the superlattice due to the transfer of spin angular momentum to the lattice. Our findings shed light on the intricate interplay of electronic and magnetic phenomena in this strongly correlated material system, suggesting a promising avenue for efficient control of two-dimensional ferromagnetic states at oxide interfaces using ultrafast electric-field pulses.

Interfacial charge transfer in oxide heterostructures gives rise to a rich variety of electronic and magnetic phenomena. Designing heterostructures where one of the thin-film components exhibits a metal-insulator transition opens a promising avenue for controlling such phenomena both statically and dynamically. In this letter, we utilize a combination of depth-resolved soft X-ray standing-wave and hard X-ray photoelectron spectroscopies in conjunction with polarization-dependent X-ray absorption spectroscopy to investigate the effects of the metal-insulator transition in $LaNiO_{3}$ on the electronic and magnetic states at the $LaNiO_{3}/CaMnO_{3}$ interface. We report on a direct observation of the reduced effective valence state of the interfacial Mn cations in the metallic superlattice with an above-critical $LaNiO_{3}$ thickness (6 u.c.) due to the leakage of itinerant Ni 3d $e_{g}$ electrons into the interfacial $CaMnO_{3}$ layer. Conversely, in an insulating superlattice with a below-critical $LaNiO_{3}$ thickness of 2 u.c., a homogeneous effective valence state of Mn is observed throughout the $CaMnO_{3}$ layers due to the blockage of charge transfer across the interface. The ability to switch and tune interfacial charge transfer enables precise control of the emergent ferromagnetic state at the $LaNiO_{3}/CaMnO_{3}$ interface and, thus, has far-reaching consequences on the future strategies for the design of next-generation spintronic devices.

Ultrashort x-ray pulses can be used to disentangle magnetic and structural dynamics and are accordingly utilized here to study the photoexcitation of NdNiO$_3$ (NNO), a model nickelate exhibiting structural and magnetic dynamics that conspire to induce an IMT. During the course of the photoinduced insulator to metal transition (IMT) with above gap excitation, we observe an ultrafast ($<$ 180 fs) quenching of magnetic order followed by a time delayed collapse of the insulating phase probed by X-ray absorption and THz transmission (~ 450 fs) that correlates with the slowest optical phonon mode involved in the structural transition. A simultaneous order-disorder response at the Ni site and displacive response at the Nd site coexist in the ultrafast magnetic response. Crucially, we observe the optical phonon through its coherent coupling with Nd magnetic order, demonstrating that the magnetic and structural degrees of freedom both contribute in driving the IMT. Density functional theory (DFT) calculations reveal a consistent scenario where optically driven inter-site charge transfer (ICT) drives a collapse of antiferromagnetic order that in turn destabilizes the charge-ordered phase resulting in an IMT. These experiments provide new modalities for control of electronic phase transitions in quantum materials based on ultrafast interplay between structural and magnetic orders created by femtosecond photoexcitation., Comment: 9 pages, 5 figures, major revision and title change from previous version

Transition metal based oxide heterostructures exhibit diverse emergent phenomena e.g. two dimensional electron gas, superconductivity, non-collinear magnetic phase, ferroelectricity, polar vortices, topological Hall effect etc., which are absent in the constituent bulk oxides. The microscopic understandings of these properties in such nanometer thick materials are extremely challenging. Synchrotron x-ray based techniques such as x-ray diffraction, x-ray absorption spectroscopy (XAS), resonant x-ray scattering (RXS), resonant inelastic x-ray scattering (RIXS), x-ray photoemission spectroscopy, etc. are essential to elucidating the response of lattice, charge, orbital, and spin degrees of freedoms to the heterostructuring. As a prototypical case of complex behavior, rare-earth nickelates (RENiO3 with RE=La, Pr, Nd, Sm, Eu, Lu) based thin films and heterostructures have been investigated quite extensively in recent years. An extensive body of literature about these systems exists and for an overview of the field, we refer the interested readers to the recent reviews Annual Review of Materials Research 46, 305 (2016) and Reports on Progress in Physics 81, 046501 (2018). In the present article, we give a brief review that concentrates on the use of synchrotron based techniques to investigate a specific set of EuNiO3/LaNiO3 superlattices, specifically designed to solve a long-standing puzzle about the origin of simultaneous electronic, magnetic and structural transitions of the RENiO3 series., Comment: Invited Review Article

On a lattice composed of triangular plaquettes where antiferromagnetic exchange interactions between localized spins cannot be simultaneously satisfied, the system becomes geometrically frustrated with magnetically disordered phases remarkably different from a simple paramagnet. Spin liquid belongs to one of these exotic states, in which a macroscopic degeneracy of the ground state gives rise to the rich spectrum of collective phenomena. Here, we report on the discovery of a new magnetic state in the heterostructures derived from a single unit cell (111)-oriented spinel CoCr2O4 sandwiched between nonmagnetic Al2O3 spacers. The artificial quasi-two-dimensional material composed of three triangle and one kagome atomic planes shows a degree of magnetic frustration which is almost two orders of magnitude enlarged compared to the bulk crystals. Combined resonant X-ray absorption and torque magnetometry measurements confirm that the designer system exhibits no sign of spin ordering down to 30 mK, implying a possible realization of a quantum spin liquid state in the two dimensional limit.

Heterostructure engineering provides an efficient way to obtain several unconventional phases of LaNiO3, which is otherwise paramagnetic, metallic in bulk form. In this work, a new class of short periodic superlattices, consisting of LaNiO3 and EuNiO3 have been grown by pulsed laser interval deposition to investigate the effect of structural symmetry mismatch on the electronic and magnetic behaviors. Synchrotron based soft and hard X-ray resonant scattering experiments have found that these heterostructures undergo simultaneous electronic and magnetic transitions. Most importantly, LaNiO3 within these artificial structures exhibits a new antiferromagnetic, charge ordered insulating phase. This work demonstrates that emergent properties can be obtained by engineering structural symmetry mismatch across a heterointerface., Comment: 4 Figures

Understanding the crystal field splitting and orbital polarization in non-centrosymmetric systems such as ferroelectric materials is fundamentally important. In this study, taking BaTiO$_3$ (BTO) as a representative material we investigate titanium crystal field splitting and orbital polarization in non-centrosymmetric TiO$_6$ octahedra with resonant X-ray linear dichroism at Ti $L_{2,3}$-edge. The high-quality BaTiO$_3$ thin films were deposited on DyScO$_3$ (110) single crystal substrates in a layer-by-layer way by pulsed laser deposition. The reflection high-energy electron diffraction (RHEED) and element specific X-ray absorption spectroscopy (XAS) were performed to characterize the structural and electronic properties of the films. In sharp contrast to conventional crystal field splitting and orbital configuration ($d_{xz}$/$d_{yz}$ $<$ $d_{xy}$ $<$ $d_{3z^2-r^2}$ $<$ $d_{x^2-y^2}$ or $d_{xy}$ $<$ $d_{xz}$/$d_{yz}$ $<$ $d_{x^2-y^2}$ $<$ $d_{3z^2-r^2}$) according to Jahn-Teller effect, it is revealed that $d_{xz}$, $d_{yz}$, and $d_{xy}$ orbitals are nearly degenerate, whereas $d_{3z^2-r^2}$ and $d_{x^2-y^2}$ orbitals are split with an energy gap $\sim$ 100 meV in the epitaxial BTO films. The unexpected degenerate states $d_{xz}$/$d_{yz}$/$d_{xy}$ are coupled to Ti-O displacements resulting from competition between polar and Jahn-Teller distortions in non-centrosymmetric TiO$_6$ octhedra of BTO films. Our results provide a route to manipulate orbital degree of freedom by switching electric polarization in ferroelectric materials.

The metal-insulator transition (MIT) of bulk rare-earth nickelates is accompanied by a simultaneous charge ordering (CO) transition. We have investigated low-frequency resistance fluctuations (noise) across the MIT and magnetic transition of [EuNiO$_3$/LaNiO$_3$] superlattices, where selective suppression of charge ordering has been achieved by mismatching the superlattice periodicity with the periodicity of charge ordering. We have observed that irrespective of the presence/absence of long-range CO, the noise magnitude is enhanced by several orders with strong non-1/$f$ ($f$ = frequency) component when the system undergoes MIT and magnetic transition. The higher order statistics of resistance fluctuations reveal the presence of strong non-Gaussian components in both cases, further indicating inhomogeneous electrical transport arising from the electronic phase separation. Specifically, we find almost three orders of magnitude smaller noise in the insulating phase of the sample without long-range CO compared to the sample with CO. These findings suggest that digital synthesis can be a potential route to implement electronic transitions of complex oxides for device application., Comment: Accepted in Phys. Rev. B

The origin of simultaneous electronic, structural and magnetic transitions in bulk rare-earth nickelates ($RE$NiO$_3$) remains puzzling with multiple conflicting reports on the nature of these entangled phase transitions. Heterostructure engineering of these materials offers unique opportunity to decouple metal-insulator transition (MIT) from the magnetic transition. However, the evolution of underlying electronic properties across these decoupled transitions remains largely unexplored. In order to address this, we have measured Hall effect on a series of epitaxial NdNiO$_3$ films, spanning a variety of electronic and magnetic phases. We find that the MIT results in only partially gapped Fermi surface, whereas full insulating phase forms below the magnetic transition. In addition, we also find a systematic reduction of the Hall coefficient ($R_H$) in the metallic phase of these films with epitaxial strain and also a surprising transition to negative value at large compressive strain. Partially gapped weakly insulating, paramagnetic phase is reminiscence of pseudogap behavior of high $T_c$ cuprates. The precursor metallic phase, which undergoes transition to insulating phase is a non-Fermi liquid with the temperature exponent ($n$) of resistivity of 1, whereas the exponent increases to 4/3 in the non-insulating samples. Such nickelate phase diagram with sign-reversal of $R_H$, pseudo-gap phase and non Fermi liquid behavior are intriguingly similar to high $T_c$ cuprates, giving important guideline to engineer unconventional superconductivity in oxide heterostructure., Comment: 8 pages, 4 figures

We report on the emergent magnetic state of (111)-oriented CoCr2O4 ultrathin films sandwiched by Al2O3 in the quantum confined geometry. At the two-dimensional crossover, polarized neutron reflectometry reveals an anomalous enhancement of the total magnetization compared to the bulk value. Synchrotron x-ray magnetic circular dichroism (XMCD) demonstrates the appearance of long-range ferromagnetic ordering of spins on both Co and Cr sublattices. Brillouin function analyses further corroborates that the observed phenomena are due to the strongly altered magnetic frustration, manifested by the onset of a Yafet-Kittel type ordering as the new ground state in the ultrathin limit, which is unattainable in the bulk.

Artificial complex-oxide heterostructures containing ultrathin buried layers grown along the pseudocubic [111] direction have been predicted to host a plethora of exotic quantum states arising from the graphene-like lattice geometry and the interplay between strong electronic correlations and band topology. To date, however, electronic-structural investigations of such atomic layers remain an immense challenge due to the shortcomings of conventional surface-sensitive probes, with typical information depths of a few Angstroms. Here, we use a combination of bulk-sensitive soft x-ray angle-resolved photoelectron spectroscopy (SX-ARPES), hard x-ray photoelectron spectroscopy (HAXPES) and state-of-the-art first-principles calculations to demonstrate a direct and robust method for extracting momentum-resolved and angle-integrated valence-band electronic structure of an ultrathin buckled graphene-like layer of $NdNiO_3$ confined between two 4-unit cell-thick layers of insulating $LaAlO_3$. The momentum-resolved dispersion of the buried Ni d states near the Fermi level obtained via SX-ARPES is in excellent agreement with the first-principles calculations and establishes the realization of an antiferro-orbital order in this artificial lattice. The HAXPES measurements reveal the presence of a valence-band (VB) bandgap of 265 meV. Our findings open a promising avenue for designing and investigating quantum states of matter with exotic order and topology in a few buried layers.

The relativistic Mott insulator Sr2IrO4 driven by large spin-orbit interaction is known for the Jeff = 1/2 antiferromagnetic state which closely resembles the electronic structure of parent compounds of superconducting cuprates. Here, we report the realization of hole-doped Sr2IrO4 by means of interfacial charge transfer in Sr2IrO4/LaNiO3 heterostructures. X-ray photoelectron spectroscopy on Ir 4f edge along with the X-ray absorption spectroscopy at Ni L2 edge confirmed that 5d electrons from Ir sites are transferred onto Ni sites, leading to markedly electronic reconstruction at the interface. Although the Sr2IrO4/LaNiO3 heterostructure remains non-metallic, we reveal that the transport behavior is no longer described by the Mott variable range hopping mode, but by the Efros-Shklovskii model. These findings highlight a powerful utility of interfaces to realize emerging electronic states of the Ruddlesden-Popper phases of Ir-based oxides., Comment: 9 pages including 3 figures and references

Almost all oxide two-dimensional electron gases are formed in SrTiO$_3$-based heterostructures and the study of non-SrTiO$_3$ systems is extremely rare. Here, we report the realization of a two-dimensional electron gas in a CaTiO$_3$-based heterostructure, CaTiO$_3$/LaTiO$_3$, grown epitaxially layer-by-layer on a NdGaO$_3$ (110) substrate via pulsed laser deposition. The high quality of the crystal and electronic structures are characterized by in-situ reflection high-energy electron diffraction, X-ray diffraction, and X-ray photoemission spectroscopy. Measurement of electrical transport validates the formation of a two-dimensional electron gas in the CaTiO$_3$/LaTiO$_3$ superlattice. It is revealed the room-temperature carrier mobility in CaTiO$_3$/LaTiO$_3$ is nearly 3 times higher than in CaTiO$_3$/YTiO$_3$, demonstrating the effect of TiO$_6$ octahedral tilts and rotations on carrier mobility of two-dimensional electron gases. Due to doped CaTiO$_3$ being an A-site polar metal, our results provide a new route to design novel A-site two-dimensional polar metals.

Perovskite nickelate heterostructure consisting of single unit cell of EuNiO$_3$ and LaNiO$_3$ have been grown on a set of single crystalline substrates by pulsed laser interval deposition to investigate the effect of epitaxial strain on electronic and magnetic properties at the extreme interface limit. Despite the variation of substrate in-plane lattice constants and lattice symmetry, the structural response to heterostructuring is primarily controlled by the presence of EuNiO$_3$ layer. In sharp contrast to bulk LaNiO$_3$ or EuNiO$_3$, the superlattices grown under tensile strains exhibit metal to insulator transition (MIT) below room temperature. The onset of magnetic and electronic transitions associated with the MIT can be further separated by application of large tensile strain. Furthermore, these transitions can be entirely suppressed by very small compressive strain. X-ray resonant absorption spectroscopy measurements reveal that such strain-controlled MIT is directly linked to strain induced self-doping effect without any chemical doping., Comment: Accepted in Phys. Rev. B

Transport and magnetoresistance measurements are performed on metallic, high-carrier density YTiO3-CaTiO3 superlattices as a probe towards the investigation of an emergent magnetic order of YTiO3. On varying the thickness of YTiO3 while keeping the CaTiO3 layer thickness constant in the superlattices, a low-temperature upturn in sheet-resistance, a non-Fermi liquid-like charge transport and positive magnetoresistance are observed. Analyses of the origin of such effects suggest that a unique antiferromagnetic order is realized in the ultra-thin, epitaxially strained YTiO3 layers, which corroborates well with some recent theoretical predictions in this regard.

Generally, lattice distortions play a key role in determining the ground states of materials. Although it is well known that trigonal distortions are generic to most two-dimensional transition metal dichalcogenides, the impact of this structural distortion on the electronic structure has not been understood conclusively. Here, by using a combination of polarization dependent X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS) and atomic multiplet cluster calculations, we have investigated the electronic structure of titanium dichalcogenides TiX2 (X=S, Se, Te), where the magnitude of the trigonal distortion increase monotonically from S to Se and Te. Our results reveal the presence of an anomalous and large crystal filed splitting. This unusual kind of crystal field splitting is likely responsible for the unconventional electronic structure of TiX2 compounds. Our results also indicate the drawback of the distorted crystal field picture in explaining the observed electronic ground state of these materials and emphasize the key importance of metal-ligand hybridization and electronic correlation in defining the electronic structures near Fermi energy.

Polar metals, commonly defined by the coexistence of polar crystal structure and metallicity, are thought to be scarce because the long-range electrostatic fields favoring the polar structure are expected to be fully screened by the conduction electrons of a metal. Moreover, reducing from three to two dimensions, it remains an open question whether a polar metal can exist. Here we report on the realization of a room temperature two-dimensional polar metal of the B-site type in tri-color (tri-layer) superlattices BaTiO$_3$/SrTiO$_3$/LaTiO$_3$. A combination of atomic resolution scanning transmission electron microscopy with electron energy loss spectroscopy, optical second harmonic generation, electrical transport, and first-principles calculations have revealed the microscopic mechanisms of periodic electric polarization, charge distribution, and orbital symmetry. Our results provide a route to creating all-oxide artificial non-centrosymmetric quasi-two-dimensional metals with exotic quantum states including coexisting ferroelectric, ferromagnetic, and superconducting phases.

Coupled transitions between distinct ordered phases are important aspects behind the rich phase complexity of correlated oxides that hinders our understanding of the underlying phenomena. For this reason, fundamental control over complex transitions has become a leading motivation of the designer approach to materials. We have devised a series of new superlattices by combining a Mott insulator and a correlated metal to form ultra-short period superlattices, which allow one to disentangle the simultaneous orderings in $RE$NiO$_3$. Tailoring an incommensurate heterostructure period relative to the bulk charge ordering pattern suppresses the charge order transition while preserving metal-insulator and antiferromagnetic transitions. Such selective decoupling of the entangled phases resolves the long-standing puzzle about the driving force behind the metal-insulator transition and points to the site selective Mott transition as the operative mechanism. This designer approach emphasizes the potential of heterointerfaces for selective control of simultaneous transitions in complex materials with entwined broken symmetries., Comment: Accepted in Phys. Rev. Lett

Unlike widely explored complex oxide heterostructures grown along [001], the study of [111]-oriented heterointerfaces are very limited thus far. One of the main challenges is to overcome the polar discontinuity that hinders the epitaxy of atomically sharp interfaces. Here, by taking the LaCoO3/SrTiO3(111) as a prototype, we show that the reconstruction, which effectively compensates the surface polarity, can stabilize the epitaxy of the heterostructure with polar discontinuity. Reconstructed substrate surface is prepared, while the growth is controlled to form reconstruction on the film surface. To suppress the chemical diffusion across the interface, the growth is interrupted between each unit cell layer to allow the lattice relaxation at a lowered temperature. In this way, high quality two-dimensional growth is realized and the heterointerfaces exhibit sharpness at the atomic scale. Our work provides a path to precisely control the growth of complex oxide heterostructures along polar orientations that exhibit emergent quantum phenomena., Comment: 12 pages, 3 figures

We report on the selective fabrication of high-quality Sr$_2$IrO$_4$ and SrIrO$_3$ epitaxial thin films from a single polycrystalline Sr$_2$IrO$_4$ target by pulsed laser deposition. Using a combination of X-ray diffraction and photoemission spectroscopy characterizations, we discover that within a relatively narrow range of substrate temperature, the oxygen partial pressure plays a critical role in the cation stoichiometric ratio of the films, and triggers the stabilization of different Ruddlesden-Popper (RP) phases. Resonant X-ray absorption spectroscopy measurements taken at the Ir $L$-edge and the O $K$-edge demonstrate the presence of strong spin-orbit coupling, and reveal the electronic and orbital structures of both compounds. These results suggest that in addition to the conventional thermodynamics consideration, higher members of the Sr$_{n+1}$Ir$_n$O$_{3n+1}$ series can possibly be achieved by kinetic control away from the thermodynamic limit. These findings offer a new approach to the synthesis of ultra-thin films of the RP series of iridates and can be extended to other complex oxides with layered structure., Comment: 7 pages, 6 figures

Epitaxial heterostructures composed of complex oxides have fascinated researchers for over a decade as they offer multiple degrees of freedom to unveil emergent many-body phenomena often unattainable in bulk. Recently, apart from stabilizing such artificial structures along the conventional [001]-direction, tuning the growth direction along unconventional crystallographic axes has been highlighted as a promising route to realize novel quantum many-body phases. Here we illustrate this rapidly developing field of geometrical lattice engineering with the emphasis on a few prototypical examples of the recent experimental efforts to design complex oxide heterostructures along the (111) orientation for quantum phase discovery and potential applications.

In all archetypical reported (001)-oriented perovskite heterostructures, it has been deduced that the preferential occupation of two-dimensional electron gases is in-plane $d_\textrm{xy}$ state. In sharp contrast to this, the investigated electronic structure of a spinel-perovskite heterostructure $\gamma$-Al$_2$O$_3$/SrTiO$_3$ by resonant soft X-ray linear dichroism, demonstrates that the preferential occupation is out-of-plane $d_\textrm{xz}$/$d_\textrm{yz}$ states for interfacial electrons. Moreover, the impact of strain further corroborates that this anomalous orbital structure can be linked to the altered crystal field at the interface and symmetry breaking of the interfacial structural units. Our findings provide another interesting route to engineer emergent quantum states with deterministic orbital symmetry., Comment: 4 figures

The superconductor-to-insulator transition (SIT) induced by means such as external magnetic fields, disorder or spatial confinement is a vivid illustration of a quantum phase transition dramatically affecting the superconducting order parameter. In pursuit of a new realization of the SIT by interfacial charge transfer, we developed extremely thin superlattices composed of high $T_c$ superconductor YBa$_2$Cu$_3$O$_7$ (YBCO) and colossal magnetoresistance ferromagnet La$_{0.67}$Ca$_{0.33}$MnO$_3$ (LCMO). By using linearly polarized resonant X-ray absorption spectroscopy and magnetic circular dichroism, combined with hard X-ray photoelectron spectroscopy, we derived a complete picture of the interfacial carrier doping in cuprate and manganite atomic layers, leading to the transition from superconducting to an unusual Mott insulating state emerging with the increase of LCMO layer thickness. In addition, contrary to the common perception that only transition metal ions may response to the charge transfer process, we found that charge is also actively compensated by rare-earth and alkaline-earth metal ions of the interface. Such deterministic control of $T_c$ by pure electronic doping without any hindering effects of chemical substitution is another promising route to disentangle the role of disorder on the pseudo-gap and charge density wave phases of underdoped cuprates., Comment: Accepted in Scientific Reports

We report on the phase diagram of competing magnetic interactions at nanoscale in engineered ultra-thin trilayer heterostructures of LaTiO$_{3}$/SrTiO$_{3}$/YTiO$_{3}$, in which the interfacial inversion symmetry is explicitly broken. Combined atomic layer resolved scanning transmission electron microscopy with electron energy loss spectroscopy and electrical transport have confirmed the formation of a spatially separated two-dimensional electron liquid and high density two-dimensional localized magnetic moments at the LaTiO$_3$/SrTiO$_3$ and SrTiO$_3$/YTiO$_3$ interfaces, respectively. Resonant soft X-ray linear dichroism spectroscopy has demonstrated the presence of orbital polarization of the conductive LaTiO$_3$/SrTiO$_3$ and localized SrTiO$_3$/YTiO$_3$ electrons. Our results provide a route with prospects for exploring new magnetic interfaces, designing tunable two-dimensional $d$-electron Kondo lattice, and potential spin Hall applications.

We report on the fabrication of all perovskite Mott insulator/band insulator YTiO3/CaTiO3 superlattices by pulsed laser deposition. The combination of in situ reflection high energy electron diffraction, X-ray diffraction, and X-ray reflectivity confirms the high quality of the films grown in a layer-by-layer mode. Electrical transport measurements reveal that a non-SrTiO3 based two dimensional electron gas system has formed at the YTiO3/CaTiO3 interface. These studies offer another route in the pursuit of complex oxide two-dimensional electron gas systems, which allows to obtain greater insights into the exotic many-body phenomena at such interfaces.

High-quality (001)-oriented (pseudo-cubic notation) ferromagnetic YTiO$_3$ thin films were epitaxially synthesized in a layer-by-layer way by pulsed laser deposition. Structural, magnetic and electronic properties were characterized by reflection-high-energy-electron-diffraction, X-ray diffraction, vibrating sample magnetometry, and element-resolved resonant soft X-ray absorption spectroscopy. To reveal ferromagnetism of the constituent titanium ions, X-ray magnetic circular dichroism spectroscopy was carried out using four detection modes probing complimentary spatial scale, which overcomes a challenge of probing ferromagnetic titanium with pure Ti3+(3d$^1$). Our work provides a pathway to distinguish between the roles of titanium and A-site magnetic rare-earth cations in determining the magnetism in rare-earth titanates thin films and heterostructures.

In response to Lu et al, (arXiv:1506.02787v1), here we present a detailed writeup concerning the questions raised in their comment on our eprint (arXiv:1505.07451). The key question raised by Lu et al was if the bulk-like charge ordered state becomes indetectable with resonant scattering due to ultrathin film thickness. In this reply, we first detail the relation of our work to past work on the same compound by Staub et al to demonstrate that the presented data are indeed sufficient to support our claims of no charge order on ultra thin films of NdNiO3 (NNO) on NdGaO3 (NGO). Further, we demonstrate that if a well defined charge ordered phase exists in ultra thin films, it is indeed resolvable such as that in EuNiO3 (ENO)., Comment: 7 pages, 1 figure

In complex materials observed electronic phases and transitions between them often involves coupling between many degrees of freedom whose entanglement convolutes understanding of the instigating mechanism. Metal-insulator transitions are one such problem where coupling to the structural, orbital, charge, and magnetic order parameters frequently obscures the underlying physics. Here, we demonstrate a way to unravel this conundrum by heterostructuring a prototypical multi-ordered complex oxide NdNiO3 in ultra thin geometry, which preserves the metal-to-insulator transition and bulk-like magnetic order parameter, but entirely suppresses the symmetry lowering and charge order parameter. These findings illustrate the utility of heterointerfaces as a powerful method for removing competing order parameters to gain greater insight into the nature of the transition, here revealing that the magnetic order generates the transition independently, leading to a purely electronic Mott metal-insulator transition., Comment: 16 pages, 4 Figures

In pursuit of creating cuprate-like electronic and orbital structures, artificial heterostructures based on LaNiO$_3$ have inspired a wealth of exciting experimental and theoretical results. However, to date there is a very limited experimental understanding of the electronic and orbital states emerging after interfacial charge-transfer and their connections to the modified band structure at the interface. Towards this goal, we have synthesized a prototypical superlattice composed of correlated metal LaNiO$_3$ and doped Mott insulator LaTiO$_{3+\delta}$, and investigated its electronic structure by resonant X-ray absorption spectroscopy combined with X-ray photoemission spectroscopy, electrical transport and theory calculations. The heterostructure exhibits interfacial charge-transfer from Ti to Ni sites giving rise to an insulating ground state with orbital polarization and $e_\textrm{g}$ orbital band splitting. Our findings demonstrate how the control over charge at the interface can be effectively used to create exotic electronic, orbital and spin states., Comment: 4 figures

High quality (1 1 1)-oriented CoCr$_2$O$_4$/Al$_2$O$_3$ heterostructures were synthesized on the sapphire (0 0 0 1) single crystal substrates in a layer-by-layer mode. The structural properties are demonstrated by $in$-$situ$ reflection high energy electron diffraction, atomic force microscopy, X-ray reflectivity and X-ray diffraction. X-ray photoemission spectroscopy confirms that the films possess the proper chemical stoichiometry. This work offers a pathway to fabricating spinel type artificial quasi-two-dimensional frustrated lattices by means of geometrical engineering.

Deterministic control over the periodic geometrical arrangement of the constituent atoms is the backbone of the material properties, that along with the interactions define the electronic and magnetic ground state. Following this notion, a bilayer of a prototypical rare-earth nickelate, NdNiO$_3$, combined with a dielectric spacer, LaAlO$_3$, has been layered along the pseudo cubic [111] direction. The resulting artificial graphene-like Mott crystal with magnetic 3$d$ electrons has antiferromagnetic correlations. In addition, a combination of resonant X-ray linear dichroism measurements and \textit{ab-initio} calculations reveal the presence of an ordered orbital pattern, which is unattainable in either bulk nickelates or nickelate based heterostructures grown along the [001] direction. These findings highlight another promising venue towards designing new quantum many-body states by virtue of geometrical engineering., Comment: Text, Figures have been modified

We report on the fabrication of high quality (1 1 1)-oriented ferrimagnetic normal spinel CoCr2O4 epitaxial thin films on single crystal Al2O3 substrates. The structural, electronic and magnetic properties were characterized by in-situ reflection high energy electron diffraction, atomic force microscopy, X-ray diffraction, X-ray photoemission spectroscopy, SQUID magnetometry and element resolved resonant X-ray magnetic scattering. The comprehensive characterization reveals that no disorder in the cation distribution or multivalency issue is present in the samples. As a result, Kagome and triangular layers are naturally formed via this specific growth approach. These findings offer a pathway to fabricate two dimensional Kagome heterostructures with novel quantum many-body phenomena by means of geometrical design., Comment: 11 pages, 4 figures

Ultra-thin films of the electron doped manganite La$_{0.8}$Ce$_{0.2}$MnO$_3$ were grown in a layer-by-layer growth mode on SrTiO$_3$ (001) substrates by pulsed laser interval deposition. High structural quality and surface morphology was confirmed by a combination of synchrotron based x-ray diffraction and atomic force microscopy. Resonant X-ray absorption spectroscopy measurements confirm the presence of Ce$^{+4}$ and Mn$^{+2}$ ions. In addition, the electron doping signature was corroborated by Hall effect measurements. All grown films show ferromagnetic ground state as revealed by both XMCD and magnetoresistance measurements and remain insulating contrary to earlier reports of metal-insulator transition. Our results hint at the possibility of electron-hole asymmetry in the colossal magnetoresistive (CMR) manganite phase diagram akin to high-$T_c$ cuprates.

We address the fundamental issue of growth of perovskite ultra-thin films under the condition of a strong polar mismatch at the heterointerface exemplified by the growth of a correlated metal LaNiO$_3$ on the band insulator SrTiO$_3$ along the pseudo cubic [111] direction. While in general the metallic LaNiO$_3$ film can effectively screen this polarity mismatch, we establish that in the ultra-thin limit, films are insulating in nature and require additional chemical and structural reconstruction to compensate for such mismatch. A combination of in-situ reflection high-energy electron diffraction recorded during the growth, X-ray diffraction, and synchrotron based resonant X-ray spectroscopy reveal the formation of a chemical phase La$_2$Ni$_2$O$_5$ (Ni$^{2+}$) for a few unit-cell thick films. First-principles layer-resolved calculations of the potential energy across the nominal LaNiO$_3$/SrTiO$_3$ interface confirm that the oxygen vacancies can efficiently reduce the electric field at the interface.

Ultra-thin tri-color (tri-layer) titanate superlattices ([3u.c. LaTiO3/2u.c. SrTiO3/3u.c. YTiO3], u.c. = unit cells) were grown in a layer-by-layer way on single crystal TbScO3 (110) substrates by pulsed laser deposition. High sample quality and electronic structure were characterized by the combination of in-situ photoelectron and ex-situ structure and surface morphology probes. Temperature-dependent sheet resistance indicates the presence of metallic interfaces in both [3u.c. LaTiO3/2u.c. SrTiO3] bi-layers and all the tri-color structures, whereas a [3u.c. YTiO3/2u.c. SrTiO3] bi-layer shows insulating behavior. Considering that in the bulk YTiO3 is ferromagnetic below 30 K, the tri-color titanate superlattices provide an opportunity to induce tunable spin- polarization into the two-dimensional electron gas (2DEG) with Mott carriers., Comment: 12 pages, 3figures, 1 table

Ultrathin epitaxial films of EuNiO3 were grown on a series of substrates traversing highly compressive (- 2.4%) to highly tensile (2.5%) lattice mismatch. X-ray diffraction measurements showed the expected c-lattice parameter shift for compressive strain, but no detectable shift for tensilely strained substrates, while reciprocal space mapping confirmed the tensile strained film maintained epitaxial coherence. Transport measurements showed a successively (from tensile to compressive) lower resistance and a complete suppression of the metalinsulator transition at highly compressive lattice mismatch. Corroborating these findings, X-ray absorption spectroscopy measurements revealed a strong multiplet splitting in the tensile samples that progressively weakens with increasing compressive strain that, combined with cluster calculations, showed enhanced covalence between Ni-d and O-p orbitals leads to the metallic state.

We report on a resonant soft X-ray spectroscopy study of the electronic and magnetic structure of the cuprate-manganite interface. Polarized X-ray spectroscopy measurements taken at the Cu L edge reveal up to a five-fold increase in the dichroic signal as compared to past experimental and theoretical values. Furthermore an increase in the degree of interlayer charge transfer up to 0.25e (where e is charge of an electron) per copper ion is observed leading to a profound reconstruction in the orbital scheme for these interfacial copper ions. It is inferred that these enhancement are related to an increase in TMI observed for manganite layers grown with rapidly modulated flux.

The epitaxial stabilization of a single layer or superlattice structures composed of complex oxide materials on polar (111) surfaces is severely burdened by reconstructions at the interface, that commonly arise to neutralize the polarity. We report on the synthesis of high quality LaNiO$_3$/mLaAlO$_3$ pseudo cubic (111) superlattices on polar (111)-oriented LaAlO$_3$, the proposed complex oxide candidate for a topological insulating behavior. Comprehensive X-Ray diffraction measurements, RHEED, and element specific resonant X-ray absorption spectroscopy affirm their high structural and chemical quality. The study offers an opportunity to fabricate interesting interface and topology controlled (111) oriented superlattices based on ortho-nickelates.

We studied an electron-induced metal-insulator transition in a two-terminal device based on oxide NdNiO3. In our device, the NdNiO3 is electrostatically doped by the voltage applied between the terminals, resulting in an asymmetric conductivity with respect to the bias polarity. The asymmetry is temperature-dependent and is most significant near the metal-insulator transition. The I-V characteristics exhibit a strong dependence both on the thermal history and the history of the applied voltage bias. Our two-terminal device represents a simple and efficient route for studies of the effect of electron doping on the metal-insulator transition., Comment: 4 pages, 5 Figures